A theory of extinction is derived which is valid within the limit of the Darwin intensity transfer equations. An expression describing the effect of n-fold rescattering within an ideal crystallite is derived, which differs from the equation given by Zachariasen because independent coordinates xl and x2 based on an external coordinate system have been used, rather than the coordinates h and t~ which are only mutually independent if the crystal is a parallelepiped with faces parallel to the incident and diffracted beams. Furthermore, the derivation of the earlier expressions is based on a generally unjustifiable reversal of the direction of the diffracted ray (interchange of t2 and t;). An exact expression is derived for the diffraction cross section o(e0 in the perfect crystallite, which contains a factor sin 20 neglected in the earlier work. As a result, the previously used classification of crystals into type I and type II becomes less well defined because at very small Bragg angles particle size always becomes the dominant effect. It is shown that the extinction factor yp (p = primary), for a perfect spherical crystallite, calculated with the present theory, is in good agreement with calculations based on the dynamical theory. Furthermore, the limiting behavior of the expressions at 20= 0 and zr justifies some of the mathematical approximations made. For a mosaic crystal the extinction coefficient y is written as y~,. Ys (s = secondary), yp is evaluated numerically from the expressions derived. An analytical expression for yp is obtained by least-squares fit to the numerical values. A similar procedure is followed for ys, in the case of a Gaussian, Lorentzian and Fresnellian distributions of the crystallites and a spherical mosaic crystal. Analysis of the results shows that the Zachariasen expression can be used for small extinction (y > 0.8), provided the 0 dependent factor is properly introduced for particle-size-affected extinction. Allowance for polarization effects in the X-ray case is discussed. Absorption effects cannot be treated separately from extinction for all but small values of 1 -y. Coefficients of the analytical extinction expressions are given for absorbing spherical crystals with/~R values <4. Application of the expressions and extension to non-spherical geometries will be treated in following publications.

Refinement of the population and radial dependence of the spherical atomic valence shell is introduced in a general crystallographic least-squares program. The radial dependence is described by an expansioncontraction parameter K, which, in the nine data sets tested, indicates contraction of positively and expansion of negatively charged atoms in agreement with theoretical concepts such as those incorporated in Slater's analytical rules for atomic orbitals. H atoms appear more contracted than concluded previously on the basis of a comparison of X-ray and neutron thermal parameters of sucrose. An average value of 1.40 for the radial contraction of H is used in structures for which no neutron thermal parameters are available. The resuiting net charges are used to calculate X-ray molecular dipole moments whose magnitude and direction are in good agreement with theoretical and other experimental results, though some differences may be expected because of matrix effects. Net molecular charges in the one-dimensional conductor TTF-TCNQ agree with results obtained earlier by direct integration of the charge density over the molecular volume. A charge transfer from Si to V in the superconducting alloy V3Si is also in agreement with earlier results.

We present the development of the extended Skyrme N2LO pseudo-potential in the case of spherical even-even nuclei calculations. The energy density functional is first presented. Then we derive the mean-field equations and discuss the numerical method used to solve the resulting fourth-order differential equation together with the behaviour of the solutions at the origin. Finally, a fitting procedure for such a N2LO interaction is discussed and we provide a first parametrization. Typical ground-state observables are calculated and compared against experimental data.